US4460729A - Polyester composition - Google Patents
Polyester composition Download PDFInfo
- Publication number
- US4460729A US4460729A US06/377,922 US37792282A US4460729A US 4460729 A US4460729 A US 4460729A US 37792282 A US37792282 A US 37792282A US 4460729 A US4460729 A US 4460729A
- Authority
- US
- United States
- Prior art keywords
- composition
- parts
- polyethylene terephthalate
- pet
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- This invention relates to thermoplastic polyester compositions which are especially useful for injection molding operations conducted at relatively low mold temperatures.
- PET polyethylene terephthalate
- relatively high mold temperatures e.g., 120°-140° C.
- Any attempt to use a lower mold temperature e.g., 100 ° C. or lower, results in the injected material being unmoldable as, for one thing, the molded article sticks in the mold and often can only be removed with great difficulty.
- the molder is forced to select more expensive materials such as polybutylene terephthalate (PBT), inasmuch as this poly(alkylene terephthalate) is easily moldable even when using mold temperatures as low as 60° C.
- PBT polybutylene terephthalate
- the time necessary for cooling the injection molded article to a temperature at which it can be removed from the mold is considerably shorter than the cooling time necessary before the PET article can be removed from its initially hotter mold. Since this shorter cooldown period of PBT results in a shorter process cycle time and a higher rate of article production, economic justification exists for its use despite its higher unit cost.
- a welcome contribution to the art would be a PET composition which can be injection molded at relatively low mold temperatures (e.g., 100 ° C. and below) to yield articles exhibiting good moldability characteristics, e.g., good mold releasability and desirable physical properties.
- thermoplastic injection moldable composition which comprises an intimate admixture of:
- a poly- ⁇ -olefin resin formed from one or more acyclic hydrocarbon ⁇ -olefins containing at least two but no more than about eight carbon atoms in the repeating unit;
- compositions may be molded at relatively low mold temperatures (e.g., in the range of about 50° C. to about 100 ° C.) without excessive sticking being encountered.
- compositions of this invention may be injected molded at even higher mold temperatures (e.g., about 100° to about 150° C.).
- compositions may additionally contain reinforcing amounts of a reinforcing filler, e.g., glass fibers.
- a reinforcing filler e.g., glass fibers.
- Other additives may also be used in the composition such as flame retardants, impact modifiers, viscosity stabilizers, color stabilizers and the like.
- the polyethylene terephthalate used herein is preferably homopolymeric PET although crystallizable PET copolymers may also be used.
- Exemplary of useful PET copolymers are those copolymers in which the copolymer contains at least 80 mol percent of repeating units derived from terephthalic acid and ethylene glycol with the remainder (20 mol percent or less) being derived from other well known acid and/or glycol components.
- Representative acid components are phthalic acid, isophthalic acid, naphthalene 1,4-or 2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, adipic acid, sebacic acid as well as their halogenated (preferably brominated) counterparts.
- the glycol components may be diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 2,2-bis(4-hydroxyphenyl) propane, 1,3-propanediol, 1,4-butanediol, dibromoneopentyl glycol, the bis(2-hydroxyethyl) ether of tetrabromobisphenol A, tetrabromo-p-xylylene glycol and the like.
- the polyethylene terephthalates used herein can be virgin PET or reclaimed PET.
- the PET used in the compositions of this invention is injection moldable and thus generally will have an intrinsic viscosity (I.V.) as low as 0.3 and preferably between about 0.4 and 1.2, and most preferably between about 0.5 and 1.0, as measured at 25° C. in a solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane.
- I.V. intrinsic viscosity
- polyethylene terephthalates in which the I.V. is in the range of 0.4 to 0.9 are most preferred.
- compositions preferably have an amount of the poly ⁇ -olefin resin within the range of from about 0.5 to about 12 parts per hundred parts of PET and an amount of the adjuvant within the range of from about 0.05 to about 5 parts per hundred parts of PET. Most preferably, the amounts of these components used fall, per hundred parts of PET, within the range of from about 2 to about 8 parts of the poly- ⁇ -olefin resin and from about 0.1 to about 3 parts of the adjuvant.
- sodium stearate is highly preferred for its synergistic coaction with the poly- ⁇ olefins of this invention.
- other alkali metal salts of substantially saturated aliphatic monocarboxylic acids will likewise perform synergistically when used pursuant to this invention.
- Exemplary of such monocarboxylic acid salts are sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium hexoate, sodium octoate, sodium decanoate, sodium laurate, potassium laurate, sodium tetradecanoate, sodium hexadecanoate and the like.
- a preferred class of adjuvants comprises the alkali metal salts of substantially saturated aliphatic monocarboxylic acids having from about 12 to about 36 carbon atoms in the molecule and of these, the alkali metal salts of the acids containing from about 16 to about 30 carbon atoms in the molecule are especially preferred.
- Potassium myristate, sodium palmitate, sodium stearate, potassium stearate, sodium behenate, and sodium montanate serve as examples of such materials.
- the potassium salts and especially the sodium salts of the above-described acids are most preferred, however, the lithium, cesium and rubidium salts, while not as available and economical, should perform satisfactorily with the ⁇ -olefin acrylic acid copolymer to achieve the moldability enhancement sought.
- the poly- ⁇ -olefin resin used as component (b) of the composition of this invention can be a homopolymer or it can be a copolymer (i.e., a polymer made from two or more non-cyclic ⁇ -olefinic hydrocarbons, each of which contains no more than about 8 carbon atoms).
- a copolymer i.e., a polymer made from two or more non-cyclic ⁇ -olefinic hydrocarbons, each of which contains no more than about 8 carbon atoms.
- those in which one of the monomers is ethylene are preferred.
- Illustrative of such resinous polymers are: ethylene, propylene, 1,6-hexadiene terpolymer, polyethylene (high, medium and low density); polypropylene; poly-4-methyl-1-pentene; poly 1-octene; ethylene-propylene copolymers; ethylidene norbornene terpolymer; ethylene-1-butene copolymers; ethylene-propylene-1-butene terpolymers, linear low-density polyethylene containing at least about 90% ethylene repeating units, and, as the balance of the repeating units, higher olefins such as butene, pentene, heptene, octene and the like; etc.
- polyethylene having a viscosity within the range of from about 150 to about 700 centipoise as measured at 140° C. with a Brookfield viscometer.
- Another poly- ⁇ -olefin which is highly preferred is amorphous, i.e., atactic, polypropylene.
- the composition of this invention may also be utilized in the composition of this invention.
- the composition additionally contains a reinforcing filler.
- This filler depending on its nature, can increase the strength and impact qualities of the PET composition.
- the use of a reinforcing filler is often required by most present day commercial usage of injection molded PET.
- any reinforcement filler can be used, e.g., fibers, whiskers, or platelets of metals, e.g., aluminum, iron or nickel, and the like, and nonmetals, e.g., ceramics, carbon filaments, silicates, asbestos, titanate whiskers, quartz, glass flakes and fibers, and the like, or mixtures thereof.
- the filler will comprise from about 10 to about 160 parts per hundred of the unreinforced polyethylene terephthalate resin. Amounts of filler, especially glass fibers, in the range of from about 30 to about 140 parts per hundred of the unreinforced PET are preferred as such compositions have particularly desirable properties. From the standpoint of ease in injection molding usage, reinforced compositions of this invention, especially those using glass fibers, preferably contain a filler constituent in an amount within the range of from about 30 to about 90 parts per hundred of the unreinforced PET.
- the preferred reinforcing fillers are glass. It is most preferred to use fibrous glass filaments of lime-aluminum borosilicate glass that are relatively soda free. This is known as "E" glass.
- E glass lime-aluminum borosilicate glass
- flame retardants may be added if the end use of the product requires the product to be possibly subjected to ignition sources.
- Flame-retarding additives which can be used for the compositions according to the invention comprise a large number of chemical compounds which are well known to those skilled in the art. In general, they contain chemical elements which are used because of their flame-retarding capacity, for example, bromine, chlorine, antimony, phosphorus and nitrogen.
- the flame-retarding additives are bromine and/or chlorine containing organic compounds (optionally used together with auxiliary compounds, such as antimony trioxide, zinc borate, etc.) or elementary phosphorus or phosphorus compounds such as ammonium polyphosphate, various bromine and/or chlorine containing organic phosphate esters, hexaphenoxyphosphazene and the like.
- impact modifiers may be added to the composition of this invention.
- suitable impact modifiers are ethylene-vinyl acetate copolymers, ethyleneacrylic acid copolymers (having some of the acid functions neutralized), ethylene-methacrylic acid copolymers (having some of the methacrylic acid functions neutralized), ethylene-alkyl acrylate-methacrylic acid terpolymer (also having some of the methacrylic acid functions neutralized), ABS, methyl methacrylate grafted polybutadiene, methyl methacrylate grafted poly(alkyl acrylates), methyl methacrylate-styrene grafted rubbers, oxidized polyethylene, styrene-butadiene-styrene (S-B-S) block copolymers, styrene-butadiene multiblock copolymers, styrene-butadiene radial block copolymers, hydrogenated S-B-
- the customary amounts of stabilizers may be added to the compositions of this invention.
- suitable stabilizers are phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with up to 6 carbon atoms in the position(s) ortho to the phenolic hydroxyl group(s); amines, preferably secondary arylamines and their derivatives; phosphates and phosphites, preferably the aryl derivatives thereof; and quinones.
- suitable stabilizers are phenols and phenol derivatives, preferably sterically hindered phenols which contain alkyl substituents with up to 6 carbon atoms in the position(s) ortho to the phenolic hydroxyl group(s); amines, preferably secondary arylamines and their derivatives; phosphates and phosphites, preferably the aryl derivatives thereof; and quinones.
- a few nonlimiting examples include
- compositions of this invention there may be additionally added ultraviolet ray absorbents, lubricants, anti-static agents, colorizing agents, antifungal agents, foaming agents, etc. depending upon the ultimate use of the molded product.
- compositions of this invention can be prepared by blending the various components in a blender, e.g., a tumble blender or a Henschel mixer, compounding the mixture in an extruder, e.g., a twin-screw 28 mm Werner-Pfleiderer extruder, and thereafter chopping the extrudate into pellets.
- a blender e.g., a tumble blender or a Henschel mixer
- an extruder e.g., a twin-screw 28 mm Werner-Pfleiderer extruder
- chopping the extrudate into pellets.
- the resultant product is suitable for use in injection molding operations. It is noteworthy that the compositions of this invention can be satisfactorily injection molded at mold temperatures less than 100 ° C. with an acceptably short cycle time and with the molded article exhibiting physical properties which are commercially attractive or which at least have commercial potential.
- the various PET compositions of these Examples were prepared by mixing the components to form a premix, compounding the premix in a single screw extruder at temperatures of about 500° F. (260° C.), and molding the pellets into an article on a reciprocating screw injection molding machine.
- the injection mold was suitably shaped and dimensioned for providing an article having the configuration shown in the FIG. 1 of the Drawing--which is a top plan view of the article.
- the mold utilized was a center gated mold having a non-moveable planar sprue side and a movable cavity side.
- the article formed by the mold has a plurality of runners, labeled A, which terminate into various test pieces.
- test piece Emanating from the center of the runner grid is a conventional tapered sprue.
- Two of the test pieces are rectangular bars and are labeled with the letter "B". These "B" bars are about six inches long, 1/2 inch wide and 1/4 inch thick.
- the test piece labeled “C” in the Figure is a rectangular bar which is 21/2 inches long, 1/2 inch wide and 1/8 inch thick.
- the two "dog bone” shaped test pieces are labeled "D” and are used for the testing of tensile properties. They measure about 61/2 inches long, 1/8 inch thick and 3/4 inch in width at each of their ends and 1/2 inch in width at their middles.
- the test piece labeled "E” is 4 inches long, 23/4 inches wide and 1/8 inch thick.
- the runners and sprue are approximately 3/8 inch in cross sectional width.
- This configuration for the test article was chosen for its com- plexity and for its yield of testable pieces which are used in accordance with well recognized standard tests. The complexity of the article configuration was also thought sufficient to give a good prediction of moldability performance of the composition when used to form typical commercial articles.
- PET Polyethylene terephthalate
- Vituf 5901 - crystalline PET having an intrinsic viscosity of 0.59 measured at 25° C. in solvent consisting of 60 percent by weight phenol and 40 percent by weight of tetrachloroethane.
- Polyethylene from Allied Chemical, Fibers and Plastic Company, Morristown, N.J. 07960, and designated as A-C 6A polyethylene.
- Linear Low Density Polyethylene from The Dow Chemical Company, Midland, Mich., 48460, and designated as Dowlex Resin 2045.
- Amorphous Polypropylene from Crowley Chemical Company, New York, N.Y., 10016 and designated as Polytac R-500.
- Sodium stearate from Witco Chemical Corporation, Organic Division, New York, N.Y. 10017 and designated as T-1 or Heat Stable grade.
- Table I reports the moldability characteristics of various compositions of this invention (Examples 1-4).
- Table II reports on the moldability of PET compositions not utilizing the combination of this invention, i.e., either the adjuvant, or the poly- ⁇ -olefin, or both constituents are missing from the composition (Comparative Examples 5-7). Moldability of the compositions was evaluated by determining "the number of sticks” (i.e., the number of times the molding cycle had to be stopped and a molded specimen physically removed from the mold) in relation to the "number of shots” (i.e., the number of injections) that were made with the given PET composition. In severe cases, removal of a stuck part required prying or chiseling; in less severe cases, removal was possible by hand.
- Table III reports the physical properties of molded articles made from the compositions of Examples 1-4.
- the mold temperature was kept at approximately 200° F. (93° C.). All parts shown in the Tables are by weight.
- Table III illustrate the good balance of physical properties exhibited by articles injection molded from compositions of this invention.
- the injection molded test specimens used to evaluate the physical properties were part of the articles produced in Examples 1-4 and were tessted according to the followig ASTM procedures:
Abstract
Description
TABLE I ______________________________________ Compositions of this Invention and Their Moldability at 93° C. Example No. 1 2 3 4 ______________________________________ PET Resin - parts 100 100 100 100 Glass Fibers - parts/100 parts PET 43 43 43 43 A-C 6A polyethylene - parts/100 parts 3.0 -- -- -- PET Polytac R-500 (Amorphous polypro- -- 3.0 -- -- pylene) - parts/100 parts PET Profax Polypropylene Grade 6523 - -- -- 3.0 -- parts/100 parts PET Dowlex Resin 2045 (Linear low density -- -- -- 3.0 polyethylene - parts/100 parts PET Sodium Stearate - parts/100 parts PET 0.5 0.5 0.5 0.5 No. of sticks/No. of shots 0/10 0/10 7/16 9/22 ______________________________________
TABLE II ______________________________________ Composition Not of this Invention and Their Moldability at 93° C. Comparative Example No. 5 6 7 ______________________________________ PET Resins - parts 100 100 100 Glass Fibers - parts/100 parts PET 43 43 43 A-C 6A polyethylene - parts/100 parts PET 3.0 -- -- Sodium Stearate - parts/100 parts PET -- 0.5 -- No. of sticks/No. of shots 10/10 10/10 10/10 ______________________________________
TABLE III __________________________________________________________________________ Compositions of this Invention and Their Physical Properties Example No. 1 2 3 4 __________________________________________________________________________ PET Resin - parts 100 100 100 100 Glass Fibers - parts/100 parts PET 43 43 43 43 Poly- α-olefin - parts/100 parts PET 3 of A-C 6A 3 of Poly- 3 of Profax 3 of Dowlex tac R-500 PP Grade 6523 2045 Sodium Stearate - parts/100 parts PET 0.5 0.5 0.5 0.5 Specific Gravity 1.609 1.566 1.567 1.573 Tensile Yield, psi 21,000 19,400 20,700 21,700 Tensile Elastic Modulus, 10.sup.3 psi 1,320 1,360 1,420 1,370 Elongation at Yield, % <10 <10 <10 N.A. Flexural Strength, psi 33,000 29,800 31,600 32,800 Flexural Elastic Modulus, 10.sup.3 psi 1,410 1,360 1,360 1,370 Izod Impact - 1/4 in. bar, ft-lb/in 1.7 1.8 1.9 1.8 Izod Impact - 1/8 in. bar, ft-lb/in 2.9 2.9 2.1 2.1 Vicat Softening Point, °C. 248 N.A. 251 N.A. Heat Deflection Temp., °C. @ 264 psi 237 235 234 238 Heat Deflection Temp., °C. @ 66 psi 249 255 255 256 Rockwell Hardness, R scale 120 121 122 121 __________________________________________________________________________ N.A. = data not available
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/377,922 US4460729A (en) | 1982-05-13 | 1982-05-13 | Polyester composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/377,922 US4460729A (en) | 1982-05-13 | 1982-05-13 | Polyester composition |
Publications (1)
Publication Number | Publication Date |
---|---|
US4460729A true US4460729A (en) | 1984-07-17 |
Family
ID=23491034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/377,922 Expired - Fee Related US4460729A (en) | 1982-05-13 | 1982-05-13 | Polyester composition |
Country Status (1)
Country | Link |
---|---|
US (1) | US4460729A (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4546126A (en) * | 1983-07-13 | 1985-10-08 | Ciba Geigy Corporation | Flame-retarding, reinforced moulding material based on thermoplastic polyesters and the use thereof |
US4826897A (en) * | 1986-12-30 | 1989-05-02 | E. I. Dupont De Nemours And Company | Process for reclaiming polyethylene terephalate scrap contaminated with chlorine-containing polymer |
US4870110A (en) * | 1986-12-30 | 1989-09-26 | E. I. Dupont De Nemours And Company | Process for reclaiming polyethylene terephthalate scrap contaminated with chlorine-containing polymer |
US5194468A (en) * | 1992-06-19 | 1993-03-16 | General Motors Corporation | High density polyethylene polyblends |
US5208277A (en) * | 1991-07-15 | 1993-05-04 | Phillips Petroleum Company | Glass reinforced blends of higher α-olefins and polyesters optionally compatibilized with carboxylated polyolefins |
US5741448A (en) * | 1996-03-14 | 1998-04-21 | Reichhold Chemicals, Inc. | Shrink-controlled resin composition |
US5763077A (en) * | 1994-08-03 | 1998-06-09 | Ykk Corporation | Linear materials with pearly luster for fasteners and method for production thereof |
US20040072000A1 (en) * | 2002-10-01 | 2004-04-15 | Kawka Dariusz Wlodzimierz | Aramid paper laminate |
US20040106723A1 (en) * | 2002-08-12 | 2004-06-03 | Yang Henry Wu-Hsiang | Plasticized polyolefin compositions |
US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
US7875670B2 (en) | 2002-08-12 | 2011-01-25 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
US8513347B2 (en) | 2005-07-15 | 2013-08-20 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
US20180273268A1 (en) * | 2015-09-30 | 2018-09-27 | Dow Global Technologies Llc | Fitment with Ethylene/a-Olefin Multi-Block Copolymer |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB993770A (en) * | 1962-07-27 | 1965-06-02 | Glanzstoff Ag | A process for the production of injection-moulded articles from aromatic polyesters |
GB1104089A (en) * | 1965-09-09 | 1968-02-21 | Algemene Kunstzijde Unie Nv | Injection moulded articles essentially consisting of polyethylene terephthalate and processes for the manufacture thereof |
GB1208585A (en) * | 1967-12-11 | 1970-10-14 | Ici Ltd | Polyester compositions |
US3575931A (en) * | 1970-04-06 | 1971-04-20 | Allied Chem | Polyethylene terephthalate molding compositions containing dispersible nucleating agents |
US3673139A (en) * | 1970-04-06 | 1972-06-27 | Sandoz Ltd | Process for the production of injection moulded and extrusion moulded polyester products |
US3769260A (en) * | 1972-06-13 | 1973-10-30 | Allied Chem | Impact-resistant polyethylene terephthalate compositions |
US4122061A (en) * | 1976-12-23 | 1978-10-24 | General Electric Company | Impact modified polyester compositions |
US4219628A (en) * | 1979-04-02 | 1980-08-26 | Eastman Kodak Company | Molding composition from polyester blends |
US4290937A (en) * | 1977-12-30 | 1981-09-22 | General Electric Company | Thermoplastic molding compositions |
US4327198A (en) * | 1981-04-24 | 1982-04-27 | Eastman Kodak Company | Polymeric molding compositions having the high impact strength |
US4327007A (en) * | 1980-12-22 | 1982-04-27 | Allied Chemical Corporation | Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent |
US4351757A (en) * | 1980-10-24 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Molding material of polyethylene terephthalate and alkai metal salt of C30 -C54 substantially aliphatic carboxylic acid |
-
1982
- 1982-05-13 US US06/377,922 patent/US4460729A/en not_active Expired - Fee Related
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB993770A (en) * | 1962-07-27 | 1965-06-02 | Glanzstoff Ag | A process for the production of injection-moulded articles from aromatic polyesters |
GB1104089A (en) * | 1965-09-09 | 1968-02-21 | Algemene Kunstzijde Unie Nv | Injection moulded articles essentially consisting of polyethylene terephthalate and processes for the manufacture thereof |
GB1208585A (en) * | 1967-12-11 | 1970-10-14 | Ici Ltd | Polyester compositions |
US3575931A (en) * | 1970-04-06 | 1971-04-20 | Allied Chem | Polyethylene terephthalate molding compositions containing dispersible nucleating agents |
US3673139A (en) * | 1970-04-06 | 1972-06-27 | Sandoz Ltd | Process for the production of injection moulded and extrusion moulded polyester products |
US3769260A (en) * | 1972-06-13 | 1973-10-30 | Allied Chem | Impact-resistant polyethylene terephthalate compositions |
US4122061A (en) * | 1976-12-23 | 1978-10-24 | General Electric Company | Impact modified polyester compositions |
US4290937A (en) * | 1977-12-30 | 1981-09-22 | General Electric Company | Thermoplastic molding compositions |
US4219628A (en) * | 1979-04-02 | 1980-08-26 | Eastman Kodak Company | Molding composition from polyester blends |
US4351757A (en) * | 1980-10-24 | 1982-09-28 | E. I. Du Pont De Nemours And Company | Molding material of polyethylene terephthalate and alkai metal salt of C30 -C54 substantially aliphatic carboxylic acid |
US4327007A (en) * | 1980-12-22 | 1982-04-27 | Allied Chemical Corporation | Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent |
US4327198A (en) * | 1981-04-24 | 1982-04-27 | Eastman Kodak Company | Polymeric molding compositions having the high impact strength |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4546126A (en) * | 1983-07-13 | 1985-10-08 | Ciba Geigy Corporation | Flame-retarding, reinforced moulding material based on thermoplastic polyesters and the use thereof |
US4826897A (en) * | 1986-12-30 | 1989-05-02 | E. I. Dupont De Nemours And Company | Process for reclaiming polyethylene terephalate scrap contaminated with chlorine-containing polymer |
US4870110A (en) * | 1986-12-30 | 1989-09-26 | E. I. Dupont De Nemours And Company | Process for reclaiming polyethylene terephthalate scrap contaminated with chlorine-containing polymer |
US5208277A (en) * | 1991-07-15 | 1993-05-04 | Phillips Petroleum Company | Glass reinforced blends of higher α-olefins and polyesters optionally compatibilized with carboxylated polyolefins |
US5194468A (en) * | 1992-06-19 | 1993-03-16 | General Motors Corporation | High density polyethylene polyblends |
US5763077A (en) * | 1994-08-03 | 1998-06-09 | Ykk Corporation | Linear materials with pearly luster for fasteners and method for production thereof |
US5945055A (en) * | 1994-08-03 | 1999-08-31 | Ykk Corporation | Process for making a filament from a polyester-polypropylene blend |
US5741448A (en) * | 1996-03-14 | 1998-04-21 | Reichhold Chemicals, Inc. | Shrink-controlled resin composition |
US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
US8217112B2 (en) | 2002-08-12 | 2012-07-10 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
US7875670B2 (en) | 2002-08-12 | 2011-01-25 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
US7985801B2 (en) | 2002-08-12 | 2011-07-26 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
US20040106723A1 (en) * | 2002-08-12 | 2004-06-03 | Yang Henry Wu-Hsiang | Plasticized polyolefin compositions |
US8211968B2 (en) | 2002-08-12 | 2012-07-03 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
US20040072000A1 (en) * | 2002-10-01 | 2004-04-15 | Kawka Dariusz Wlodzimierz | Aramid paper laminate |
US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
US8703030B2 (en) | 2003-08-12 | 2014-04-22 | Exxonmobil Chemical Patents Inc. | Crosslinked polyethylene process |
US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
US8513347B2 (en) | 2005-07-15 | 2013-08-20 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
US20180273268A1 (en) * | 2015-09-30 | 2018-09-27 | Dow Global Technologies Llc | Fitment with Ethylene/a-Olefin Multi-Block Copolymer |
US10486880B2 (en) * | 2015-09-30 | 2019-11-26 | Dow Global Technologies, Llc | Fitment with ethylene/α-olefin multi-block copolymer |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4460729A (en) | Polyester composition | |
US4035333A (en) | Flame-resistant resin composition | |
US4486561A (en) | Injection-moldable thermoplastic polyester composition | |
US4536531A (en) | Polyester resin composition | |
US4215032A (en) | Polyester composition | |
US4530953A (en) | Polyester resin composition having an improved mold release property | |
JPH0118101B2 (en) | ||
EP0270366A2 (en) | Novel flame retardant | |
US5219941A (en) | High impact polyester/ethylene copolymer blends | |
US4440889A (en) | Polyethylene terephthalate molding compositions | |
US4346195A (en) | Polyethylene terephthalate blends | |
US5428086A (en) | Poly(1,4-cyclohexylenedimethylene terephthalate) with improved melt stability | |
US4140671A (en) | Warp-resistant flame-retarded reinforced thermoplastic compositions | |
US4539352A (en) | Injection-moldable thermoplastic polyester composition | |
US4385144A (en) | Polyester composition | |
US4483949A (en) | Polyethylene terephthalate blends | |
WO1993015148A1 (en) | Reinforced molding composition based on poly(1,4-cyclohexylene dimethylene terephthalate) containing a high molecular weight aliphatic polyester | |
EP0071773A2 (en) | Molded articles of improved impact resistance and compositions thereof | |
US4124652A (en) | Thermoplastic molding composition | |
EP0073042B1 (en) | Polyester composition | |
US4526923A (en) | Polyethylene terephthalate blends | |
CA1082394A (en) | Thermoplastc molding composition | |
US4506050A (en) | Polyethylene terephthalate molding compositions | |
GB1595039A (en) | Thermoplastic polyesters | |
US4104242A (en) | Reinforced thermoplastic polyester compositions having improved high voltage breakdown resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ETHYL CORPORATION, RICHMOND, VA., A VA CORP. Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:BOOKS, JEFFREY T.;REEL/FRAME:004252/0679 Effective date: 19820503 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: ALBERMARLE CORPORATION, VIRGINIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ETHYL CORPORATION;REEL/FRAME:007109/0340 Effective date: 19940228 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19960717 |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |